U.S. patent number 9,212,272 [Application Number 14/146,805] was granted by the patent office on 2015-12-15 for organic colouring agents and coloured polymer compositions with a high stability to weathering.
This patent grant is currently assigned to Bayer MaterialScience AG. The grantee listed for this patent is Bayer MaterialScience AG. Invention is credited to Alexander Meyer, Jorg Reichenauer, Michael Wagner.
United States Patent |
9,212,272 |
Meyer , et al. |
December 15, 2015 |
Organic colouring agents and coloured polymer compositions with a
high stability to weathering
Abstract
The present invention relates to organic coloring agents with a
high color stability to weathering for thermoplastics. The
invention furthermore relates to a polymer composition containing
at least one thermoplastic and at least one organic coloring agent,
preferably a combination of at least two organic coloring agents,
of a specific structure. The invention moreover relates to the use
of the coloring agents according to the invention for coloring
polymer compositions, in particular for transparent formulations
such as are required for the production of panes for use in
buildings, motor vehicles and track vehicles or aircraft.
Inventors: |
Meyer; Alexander (Dusseldorf,
DE), Wagner; Michael (Moers, DE),
Reichenauer; Jorg (Krefeld, DE) |
Applicant: |
Name |
City |
State |
Country |
Type |
Bayer MaterialScience AG |
Leverkusen |
N/A |
DE |
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Assignee: |
Bayer MaterialScience AG
(Leverkusen, DE)
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Family
ID: |
43737303 |
Appl.
No.: |
14/146,805 |
Filed: |
January 3, 2014 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20140121309 A1 |
May 1, 2014 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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13326438 |
Dec 15, 2011 |
8641784 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08K
5/17 (20130101); C09B 67/0034 (20130101); C09B
47/0673 (20130101); C09B 5/48 (20130101); C09B
67/0033 (20130101); C09B 47/30 (20130101); C09B
47/0678 (20130101); C09B 47/24 (20130101); C09B
47/065 (20130101); C09B 5/16 (20130101); C09B
47/12 (20130101); C08K 5/3465 (20130101); C09B
57/08 (20130101); C09B 47/062 (20130101); C08K
5/18 (20130101) |
Current International
Class: |
B60J
1/00 (20060101); C08K 5/18 (20060101); C09B
47/12 (20060101); C09B 47/24 (20060101); C09B
47/30 (20060101); C09B 57/08 (20060101); C09B
67/22 (20060101); C09B 5/16 (20060101); C08K
5/17 (20060101); D06P 1/81 (20060101); D06P
1/16 (20060101); C09B 47/06 (20060101); D06P
3/52 (20060101); D06P 3/54 (20060101); C08K
5/3465 (20060101); C09B 5/48 (20060101); C09B
47/067 (20060101) |
Field of
Search: |
;8/506,626,628,675,685,686,689 ;296/84.1 |
References Cited
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.
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|
Primary Examiner: Khan; Amina
Attorney, Agent or Firm: Drinker Biddle & Reath LLP
Parent Case Text
RELATED APPLICATIONS
This application is a continuation of U.S. patent application Ser.
No. 13/326,438, now U.S. Pat. No. 8,641,784 which claims benefit of
Italian Application No. RM2010A000670, filed Dec. 17, 2010, which
is incorporated by reference herein.
Claims
The invention claimed is:
1. A transparent polycarbonate composition comprising a colouring
agent combination of the structures selected from the group
consisting of: XIV. (3), (4), (7) XV. (3), (5), (7) XXI. (7), (4)
and XXII. (7), (5) and mixture thereof, wherein the structures are
as follows: ##STR00015## wherein R is selected from the group
consisting of H and the p-methylphenylamine radical; ##STR00016##
wherein R3 is a halogen; n=4; ##STR00017## wherein R1 and R2,
independently of one another, represent a linear or branched alkyl
radical, or halogen; n represents a natural number between 0 and 4,
wherein the colouring agent composition is used in amounts, based
on the particular individual components, of from 0.000001 wt. % to
1 wt. %, based on the total polymer composition, and wherein the
change in the colour value E after 3,000 h of artificial weathering
with exposure to xenon light at 0.75 W is less than 3.0.
2. The composition according to claim 1, wherein the colouring
agent of the structure (7) has a bulk volume of 2 l/kg to 10 l/kg,
a specific surface area of 5 m.sup.2/g to 60 m.sup.2/g and a pH of
from 4 to 9.
3. The composition according to claim 1, wherein the composition
comprises at least one colouring agent chosen from the structures 3
and at least one colouring agent chosen from the structures 4.
4. The composition according to claim 3, wherein the colouring
agents of structures 3 are present in a ratio to the colouring
agents of structures 4 of from 1:3 to 3:1.
5. The composition according to claim 1, wherein the composition
further comprises inorganic or organic IR absorbers, UV absorbers
and/or carbon black.
6. A process for preparing a weathering-stable, transparent,
thermoplastic polymer composition which comprises mixing the
transparent polycarbonate composition according to claim 1.
7. A vehicle pane comprising the composition according to claim
1.
8. The vehicle pane according to claim 7, wherein the vehicle pain
comprises a scratch-resistant coating which comprises UV absorbers.
Description
BACKGROUND
Embodiments of the present invention relate to organic colouring
agents with a high colour stability to weathering for
thermoplastics.
Embodiments of the invention furthermore relate to a polymer
composition containing at least one thermoplastic and at least one
organic colouring agent, preferably a combination of at least two
organic colouring agents, of a specific structure.
Embodiments of the invention furthermore relate to the use of the
colouring agents according to the invention for colouring polymer
compositions, in particular for transparent formulations such as
are required for the production of panes for use in buildings,
motor vehicles and track vehicles or aircraft.
Embodiments of the present invention moreover relate to a process
for the preparation of thermoplastic polymer compositions
containing the colouring agent according to the invention or the
colouring agent combination according to the invention.
Embodiments of the present invention furthermore provides the
products, shaped articles or shaped objects produced from the
thermoplastic polymer compositions coloured according to the
invention.
The colouring of plastics is known per se.
Nevertheless, there has hitherto been a lack of colouring agent
combinations, in particular for transparent formulations, which
render possible a neutral colour formulation--e.g. a grey
colour--and have an excellent stability to weathering for uses with
high optical requirements. Uses with correspondingly high
requirements of the colouring agent combinations used include,
inter alia, transparent ready-made parts for automobile glazing
which can be coloured to a varying degree depending on the use.
Because of the long life of motor vehicles, in this context it is
important in particular in the field of expensive automobiles for
the desired high quality colour impression of the material to be
retained without noticeable losses over the period of the useful
life.
Glazing produced from compositions containing transparent
thermoplastic polymers, such as e.g. polycarbonate, offers many
advantages over conventional glazing of glass for use in the
vehicle sector and for buildings. These include e.g. increased
fracture-proof properties and/or saving in weight, which in the
case of automobile glazing renders possible a higher safety of
passengers in the event of traffic accidents and a lower fuel
consumption. Finally, transparent materials which contain
transparent thermoplastic polymers allow a considerably greater
freedom of design due to the simpler formability.
Panes which are employed in the motor vehicle, track vehicle and
aircraft or in the infrastructure sector must furthermore have a
long life and should not become brittle during this life. The
colour and transparency should moreover not change or change only
slightly over the life, as is the case also for the IR protection
properties with an appropriate IR protection finish of the panes,
i.e. protection from thermal radiation. The pane must furthermore
have an adequate scratch resistance.
Because of the long life required, glass is often employed as the
glazing material. Glass is insensitive to UV radiation, has a low
susceptibility to scratching and does not change its mechanical
properties over long periods of time. Since inorganic oxides, such
as e.g. iron oxide, are employed as pigments and IR absorbers, the
IR and colour properties also remain practically unchanged over
long periods of time. Nevertheless, the use of these pigments in
thermoplastic materials is not possible, since it leads to clouding
and/or degradation of the corresponding matrix.
On the basis of the advantages described above for plastics, there
is therefore the need for materials which have both the good
physical properties of thermoplastics and the high colour stability
of correspondingly coloured glasses.
Among the transparent thermoplastics, polymers based on
polycarbonate and polymethyl methacrylate (PMMA), for example, are
particularly suitable for use as glazing material. Due to the high
toughness, polycarbonate in particular has a very good profile of
properties for such intended uses.
In order to improve the longevity of thermoplastic materials, it is
known to provide these with UV protection and/or scratch-resistant
coatings. A large number of colouring agents which have a high
fastness to light are moreover known.
It has been found, nevertheless, that the thermoplastic
compositions mentioned in the prior art are only inadequately
suitable if an exceptionally high colour stability is required.
This is the case e.g. if glass panes and transparently coloured
panes of thermoplastic material are used together in construction.
It is found here that the colour stability of glass is superior to
that of the thermoplastic material. Colour deviations are striking
in particular if these materials are used side by side in
construction.
Bleaching out of colouring agents not only leads to the change in
the colour properties, but also leads to a higher energy
transmission occurring, since about 50% of the energy transmitted
through a pane originates from the visual range of the solar
spectrum. The latter is undesirable especially in the field of
automobile and building glazing, since the particular inside
temperature is thereby influenced.
It may furthermore be necessary to configure the colouring of the
shaped article in a neutral colour, since the atmosphere of the
interior or of the interior furnishings is influenced by an
intensely coloured pane. As a rule, a grey of neutral colour is
preferred. In certain embodiments, the colouring can be changed
towards a blue-grey, a green-grey, red-grey or yellow-grey.
The composition must be processable under the conventional
temperatures for thermoplastics, without the colour or other
optical properties changing significantly during processing.
Many dyestuffs have been described as particularly fast to light
and therefore also as stable in the prior art. The fastness to
light (determined at 1/3 standard depth with 1% TiO.sub.2 (for
Polystyrol 2% TiO.sub.2 in accordance with DIN EN ISO 4892-2;
transparent dyeings with 0.05% of dyestuff; evaluated according to
an 8-level blue scale) of the so-called Macrolex dyestuffs (Lanxess
Data Sheets, Technical Information, Lanxess Deutschland GmbH,
Functional Chemicals, High Performance Additives, Colorants, 51369
Leverkusen, Germany), such as e.g. the dyestuffs Macrolex.RTM. Blue
RR (Solvent Blue 97), Macrolex.RTM. Violet 3R (Solvent Violet 36),
which are envisaged for use in polycarbonate, has been classified
with 7-8 (8=maximum value). Nevertheless, it was found in the
context of the present experiments that colouring agents formally
classified as fast to light do not have the stability according to
the invention during weathering in polycarbonate compositions.
Rather, it has been found that only a very small number of
colouring agents of a specific structure are suitable. In
particular, specific combinations are suitable for achieving the
present object.
There was therefore the object of providing colouring agents or a
colouring agent combination with a high colour stability to
weathering for thermoplastic polymers. In this context, the visual
colour impression of the coloured thermoplastic polymer composition
should change only slightly over life.
It was moreover an object of the present invention here to meet the
following prerequisites in the case of transparently coloured
thermoplastic polymer compositions:
The change in the colour values .DELTA.E after 3,000 h of
artificial weathering with exposure to xenon light at 0.75 W should
be less than 5.0, preferably less than 4.0, particularly preferably
less than 3.0. Furthermore, the visual colour impression, which
means in particular streaks and points of high colour
concentrations, also should not change.
In a particular embodiment, a neutral grey colour with colour
values of a*=0.+-.5 and b*=0.+-.5, in particular a*=0.+-.4 and
b*=0.+-.4 is preferred.
In the context of the present invention, transparency is understood
as meaning that the background when viewed through the transparent
material, e.g. in the form of a corresponding shaped article, can
be clearly detected. Mere transparency to light, such as e.g. in
the case of frosted glass, through which the background appears
only blurred, is not sufficient to describe the corresponding
material as transparent. Transparent thermoplastic polymers or the
thermoplastic polymer compositions in the context of the present
invention furthermore have an initial clouding before weathering of
less than 5.0%, preferably 4.0%, more preferably less than 3.0%,
particularly preferably less than 2.0%.
A further object of the present invention was to provide a process
for the preparation of thermoplastic polymer compositions
containing the organic colouring agents according to the invention
or the organic colouring agent combination.
It was furthermore the object of the present invention to provide
coloured thermoplastic polymer compositions containing at least one
organic colouring agent or one organic colouring agent combination
for the production of multi-layer articles, mouldings and
ready-made parts.
Surprisingly, it has been possible to achieve objects of the
invention by the organic colouring agents according to the
invention or the organic colouring agent combinations according to
the invention and the thermoplastic polymer compositions according
to the invention prepared using the organic colouring agents
according to the invention or the organic colouring agent
combinations according to the invention.
BRIEF DESCRIPTION OF PREFERRED EMBODIMENTS
An embodiment of the present invention provides a colouring agent
composition comprising a colouring agent or a colouring agent
combination of the structures selected from the group consisting
of: I. (1a) and/or (1b), (4), (2a) and/or (2b) II. (1a) and/or
(1b), (5), (2a) and/or (2b) III. (1a) and/or (1b), (7) IV. (1a)
and/or (1b), (4), (7) V. (1a) and/or (1b), (5), (7) VI. (4), (2a)
and/or (2b) VII. (5), (2a) and/or (2b) VIII. (2a) and/or (2b), (4),
(6) IX. (2a) and/or (2b), (5), (6) X. (3), (4) XI. (3), (5) XII.
(3), (4), (6) XIII (3), (5), (6) XIV. (3), (4), (7) XV. (3), (5),
(7) XVI. (3), (4), (2a) and/or (2b) XVII. (3), (5), (2a) and/or
(2b) XVIII. (6), (1a) and/or (1b) XIX. (6), (1a) and/or (1b), (7)
XX. (1a) and/or (1b), (8) XXI. (7), (4) XXII. (7), (5) XVIII. (1a)
and/or (1b), XXIV. (2a) and/or (2b), XXV. (7) XXVI. (2a) and/or
(2b), (7).
wherein the structures are as follows:
##STR00001##
wherein Ra and Rb, independently of one another, represent a linear
or branched alkyl radical, or halogen; n, independently of the
particular R, represents a natural number between 0 and 3, wherein
for n=0 the radical is hydrogen;
##STR00002##
wherein Rc and Rd, independently of one another, represent a linear
or branched alkyl radical, or halogen; n, independently of the
particular R, represents a natural number between 0 and 3, wherein
for n=0 the radical is hydrogen;
##STR00003##
wherein R is selected from the group consisting of H and the
p-methylphenylamine radical;
##STR00004##
wherein R3 is a halogen; n=4;
##STR00005##
wherein R1 and R2, independently of one another, represent a linear
or branched alkyl radical, or halogen; n represents a natural
number between 0 and 4;
##STR00006##
wherein the radicals R(5-20), independently of one another,
represent hydrogen, methyl, ethyl, propyl, isopropyl, butyl,
isobutyl, tert-butyl, pentyl, neopentyl, hexyl, thexyl, fluorine,
chlorine, bromine, sulfone or CN, and M, represents aluminium,
nickel, cobalt, iron, zinc, copper or manganese.
Another embodiment of the present invention is the above
composition, wherein the composition comprises at least one
colouring agent of the structures (1a), (1b), (2a), (2b) or
(7).
Another embodiment of the present invention is the above
composition, wherein the colouring agent of the structure (7) has a
bulk volume of 2 l/kg to 10 l/kg, a specific surface area of 5
m.sup.2/g to 60 m.sup.2/g and a pH of from 4 to 9.
Another embodiment of the present invention is the above
composition, wherein the composition comprises the colouring agents
of the structures (1a) and (1b) and/or (2a) and (2b) in a 1:1
isomer mixture.
Another embodiment of the present invention is the above
composition, wherein the composition comprises the colouring agents
of the structures (1a) and (1b) and/or (2a) and (2b) in each case
only as a pure isomer.
Another embodiment of the present invention is the above
composition, wherein the composition comprises at least one
colouring agent chosen from the structures 1 to 3 and at least one
colouring agent chosen from the structures 4 to 8.
Another embodiment of the present invention is the above
composition, wherein the colouring agents of structures 1 to 3 are
present in a ratio to the colouring agents of structures 4 to 8 of
from 1:3 to 3:1.
Yet another embodiment of the invention is a process for preparing
a weathering-stable, transparent, thermoplastic polymer composition
which comprises using the above colouring agent composition.
Yet another embodiment of the invention is a transparent
thermoplastic polymer composition comprising the above colouring
agent composition.
Another embodiment of the invention is the above polymer
composition, wherein components a) and b) are used in the
thermoplastic polymer composition in amounts, based on the
particular individual components, of from 0.000001 wt. % to 1 wt.
%, based on the total polymer composition.
Another embodiment of the invention is the above polymer
composition, wherein the thermoplastic comprises a
polycarbonate.
Another embodiment of the invention is the above polymer
composition, wherein the polymer composition further comprises an
inorganic or organic IR absorbers, UV absorbers and/or carbon
black.
Yet another embodiment of the invention is a vehicle pane
comprising the above colouring agent composition.
Another embodiment of the invention is the above vehicle pane,
wherein the vehicle pain comprises a scratch-resistant coating
which comprises UV absorbers.
Another embodiment of the invention is the above vehicle pane,
wherein the vehicle pane is a polycarbonate pane and the change in
the colour value E after 3,000 h of artificial weathering with
exposure to xenon light at 0.75 W is less than 5.0.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
As used herein, the singular terms "a" and "the" are synonymous and
used interchangeably with "one or more" and "at least one," unless
the language and/or context clearly indicates otherwise.
Accordingly, for example, reference to "a colouring agent" herein
or in the appended claims can refer to a single colouring agent or
more than one colouring agent. Additionally, all numerical values,
unless otherwise specifically noted, are understood to be modified
by the word "about."
Colouring agents or colouring agent combinations according to the
invention are the following colouring agents or combinations
(commas are to be read as "and"): I. (1a) and/or (1b), (4), (2a)
and/or (2b) II. (1a) and/or (1b), (5), (2a) and/or (2b) III. (1a)
and/or (1b), (7) IV. (1a) and/or (1b), (4), (7) V. (1a) and/or
(1b), (5), (7) VI. (4), (2a) and/or (2b) VII. (5), (2a) and/or (2b)
VIII. (2a) and/or (2b), (4), (6) IX. (2a) and/or (2b), (5), (6) X.
(3), (4) XI. (3), (5) XII. (3), (4), (6) XIII (3), (5), (6) XIV.
(3), (4), (7) XV. (3), (5), (7) XVI. (3), (4), (2a) and/or (2b)
XVII. (3), (5), (2a) and/or (2b) XVIII. (6), (1a) and/or (1b) XIX.
(6), (1a) and/or (1b), (7) XX. (1a) and/or (1b), (8) XXI. (7), (4)=
XXII. (7), (5)= XXIII. (1a) and/or (1b), XXIV. (2a) and/or (2b),
XXV. (7) XXVI. (2a) and/or (2b), (7), wherein the abovementioned
structures are defined as follows: a)
##STR00007## wherein
Ra and Rb independently of each other represent a linear or
branched alkyl radical, or halogen, preferably represent methyl,
ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl,
neopentyl, hexyl, thexyl, or Cl, more preferably methyl, Cl and
particularly preferably Cl.
n independently of the particular R represents a natural number
between 0 and 3, where for n=0 the radical is hydrogen.
In a preferred embodiment, Ra and/or Rb are Cl and are in the o
and/or p positions relative to the carbon atoms which carry the
amine functionalities, such as e.g. di-orthochloronaphthaleno,
di-ortho, mono-para-chloronaphthaleno, and mono-ortho-naphthaleno.
Furthermore, in a preferred embodiment Ra and Rb each represent a
tert-butyl radical, which is preferably in the meta position
relative to the carbon atoms which carry the nitrogen
functionalities.
In a particularly preferred embodiment, n=0 in all the rings, so
that all the Ra and Rb.dbd.H.
##STR00008## wherein
Rc and Rd independently of each other represent a linear or
branched alkyl radical, or halogen, preferably represent methyl,
ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl,
neopentyl, hexyl, thexyl, or Cl, more preferably methyl, Cl and
particularly preferably Cl.
n independently of the particular R represents a natural number
between 0 and 3, where for n=0 the radical is hydrogen.
In a preferred embodiment, Rc and/or Rd are Cl and are in the o
and/or p positions relative to the carbon atoms which carry the
amine functionalities, such as e.g. di-orthochloronaphthaleno,
di-ortho, mono-para-chloronaphthaleno, and mono-ortho-naphthaleno.
Furthermore, in a preferred embodiment Rc and Rd each represent a
tert-butyl radical, which is preferably in the meta position
relative to the carbon atoms which carry the nitrogen
functionalities.
In a particularly preferred embodiment, n=0 in all the rings, so
that all the Rc and Rd.dbd.H.
The structures (1a) and (1b), and (2a) and (2b) behave as isomers
with respect to one another. The particular isomers can be employed
by themselves or in a mixture. In a particular embodiment, a 1:1
isomer mixture (based on the particular amount of the isomer in the
isomer mixture in wt. %) of (1a) and (1b), or (2a) and (2b) is
employed.
The preparation of such colouring agents has been described e.g. in
DE 2148101 or WO 2009 074504 A1.
Preferably, the composition according to the invention contains at
least one colouring agent of the structures (1a), (1b), (2a) and
(2b), of these the colouring agents of the structures (1a) and (1b)
being particularly preferred.
In a further embodiment, the structures (1a), (1b), (2a) and (2b)
are employed as in each case pure isomers, it being possible for
the pure isomers to be obtained, for example, by preparative
HPLC.
##STR00009## R is chosen from the group which consists of H and the
p-methylphenylamine radical; preferably, R.dbd.H.
Such colouring agents are obtainable e.g. from Lanxess AG under the
trade name Macrolex.RTM. Violet B. In a particular embodiment, no
colouring agent of the structure (3) is employed.
and
b)
##STR00010## wherein R3 preferably represents halogen, and
particularly preferably Cl, wherein particularly preferably n=4. An
embodiment where n=0, so that R3=H, is more preferred.
Such colouring agents are obtainable e.g. from Lanxess AG under
Macrolex.RTM. Orange 3G or Macrolex.RTM. Red EG.
In this context, if R3 represents Cl and n=4, instead of the
colouring agent of the structure (4) the colouring agent with the
structure (5) can be employed in order to achieve the same colour
properties:
##STR00011##
Such colouring agents are obtainable e.g. from Lanxess AG under the
trade name Macrolex.RTM. Red E2G.
##STR00012##
Such colouring agents are obtainable e.g. from Lanxess AG under the
trade name Macrolex.RTM. Green G.
##STR00013## wherein
R1 and R2 independently of each other represent a linear or
branched alkyl radical, or halogen, preferably represent methyl,
ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl,
neopentyl, hexyl, thexyl, or Cl, more preferably methyl, Cl and
particularly preferably Cl.
n represents a natural number between 0 and 4.
In a particularly preferred embodiment, n=0 in all the rings, so
that all the R1 and R2=H.
Colouring agents of this structure (7) are commercially obtainable
under the Paliogen Blue series of BASF AG.
If colouring agents of the structure (7) are used, the pigments
which have a bulk volume (determined in accordance with DIN ISO
787-11) of 2 l/kg-10 l/kg, preferably 3 l/kg-8 l/kg, a specific
surface area (determined in accordance with DIN 66132) of 5
m.sup.2/g-60 m.sup.2/g, preferably 10 m.sup.2/g-55 m.sup.2/g, and a
pH (determined in accordance with DIN ISO 787-9) of 4-9 are
particularly preferred.
##STR00014##
The radicals R(5-20) are each independently of each other hydrogen,
methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl,
pentyl, neopentyl, hexyl, thexyl, fluorine, chlorine, bromine,
sulfone, CN.
Preferably, R(5-20) is the same in all positions. More preferably,
R(5-20) is H in all positions. In an alternative embodiment,
R(5-20) is Cl in all positions.
M is preferably aluminium (where R.dbd.H: aluminium phthalocyanine,
CAS: 14154-42-8). nickel (where R.dbd.H: nickel phthalocyanine,
CAS: 14055-02-8), cobalt (where R.dbd.H: cobalt phthalocyanine,
CAS: 3317-67-7), iron (where R.dbd.H: iron phthalocyanine, CAS:
132-16-1), zinc (where R.dbd.H: zinc phthalocyanine, CAS:
14320-04-08), copper (where R.dbd.H: copper phthalocyanine, CAS:
147-14-8; where R.dbd.H and Cl: polychloro-copper phthalocyanine,
CAS: 1328-53-6; where R.dbd.Cl: hexadecachlorophthalocyanine, CAS:
28888-81-5; where R.dbd.Br: hexadecabromophthalocyanine, CAS:
28746-04-5), manganese (where R.dbd.H: manganese phthalocyanine,
CAS: 14325-24-7).
The combination of M=Cu and R.dbd.H for all positions is
particularly preferred. A compound of the structure (8b) where M=Cu
and R(5-20)=H is thus obtainable from BASF AG Ludwigshafen as
Heliogen.RTM. Blue K 6911D or Heliogen.RTM. Blue K 7104 KW.
Compounds of the structure (8a) are obtainable e.g. from BASF AG,
Ludwigshafen as Heliogen.RTM. Blue L 7460.
Of the structures (4), (6), (7) and (8a) or (8b), the use of the
structures (4), (7) and (8b) is particularly preferred, it being
possible, as described above, for the structure (4) to be replaced
by structure (5) under the prerequisites described. The use of
colouring agents of the structure (7) is very particularly
preferred. In a specific embodiment of the present invention, with
respect to the organic colouring agents according to the invention
the sole use of colouring agents of the structure (7) is
particularly preferred,
A particularly preferred group of colouring agent combinations
contains no colouring agents of the structure (3).
While in an alternative embodiment colouring agent combinations
with at least in each case one colouring agent from the groups a)
and b) are preferably employed, in deviation from this colouring
agent combinations according to VC and XXII can be used in a
particular embodiment.
In this context, the explicit colouring agent structures mentioned
as preferred among the components a) and b) are correspondingly
preferably employed in these particularly suitable colouring agent
combinations.
In a furthermore preferred embodiment, the colouring agents of the
structures 1-3 are present in a ratio to the colouring agents of
the structures 4-8 of from 1:3 to 3:1, preferably in a ratio of
from 1:2 to 2:1.
The organic colouring agents disclosed as components a) and b) in
the context of the present invention can be used in thermoplastic
polymer compositions in amounts, based on the particular individual
component, of from 0.000001 wt. % to 1.000000 wt. %, preferably
from 0.00005 wt. % to 0.50000 wt. % and particularly preferably
from 0.0001 wt. % to 0.1000 wt. %.
In a specific embodiment for transparently coloured thermoplastic
polymer compositions, the organic colouring agents according to the
invention are used in the thermoplastic polymer compositions in
amounts, based on the particular individual component, of from
0.00001 wt. % to 0.30000 wt. %, preferably from 0.00005 wt. % to
0.10000 wt. % and particularly preferably from 0.00010 wt. % to
0.05000 wt. %.
The amounts stated in wt. % relate here to a resulting polymer
composition containing the organic colouring agents or organic
colouring agent combinations according to the invention.
In a preferred embodiment, the colouring agent compositions
according to the invention comprise only compounds of the
abovementioned structures 1-8.
The thermoplastic polymer compositions according to the invention
containing the organic colouring agents or organic colouring agent
combinations according to the invention are based here on the
polymer component c).
The Polymer Component c) Contains:
a thermoplastic, preferably transparent thermoplastic, preferably
polycarbonate, copolycarbonate, polyester carbonate, polystyrene,
styrene copolymers, aromatic polyester, such as polyethylene
terephthalate (PET), PET/cyclohexanedimethanol copolymer (PETG),
polyethylene naphthalate (PEN), polybutylene terephthalate (PBT),
cyclic polyolefin, poly- or copolyacrylates and poly- or
copolymethacrylate, such as e.g. poly or copolymethyl methacrylates
(such as PMMA) and copolymers with styrene, such as e.g.
transparent polystyrene/acrylonitrile (PSAN), thermoplastic
polyurethanes, polymers based on cyclic olefins (e.g. TOPAS.RTM., a
commercial product from Ticona), more preferably polycarbonate,
copolycarbonate, polyester carbonate, aromatic polyester or
polymethyl methacrylate, or mixtures of the components mentioned,
and particularly preferably polycarbonate and copolycarbonate, the
transparent thermoplastic being added in an amount such that this
gives 100 wt. % with all the other components.
Mixtures of several transparent thermoplastic polymers are also
possible, especially if they are miscible with one another to give
transparent mixtures, a mixture of polycarbonate with PMMA (more
preferably with PMMA <2 wt. %) or polyester being preferred in a
specific embodiment.
A further specific embodiment contains in this connection a mixture
of polycarbonate and PMMA with less than 2.0%, preferably less than
1.0%, more preferably less than 0.5%, wherein it contains at least
0.01% of PMMA, based on the amount of polycarbonate, the PMMA
preferably having a molecular weight of <40,000 g/mol. In a
particularly preferred embodiment, the content of PMMA is 0.2% and
particularly preferably 0.1%, based on the amount of polycarbonate,
the PMMA preferably having a molecular weight of <40,000
g/mol.
An alternative further specific embodiment contains a mixture of
PMMA and polycarbonate with less than 2%, preferably less than 1%,
more preferably less than 0.5%, still more preferably with 0.2% and
particularly preferably 0.1% of polycarbonate, based on the amount
of PMMA.
Suitable polycarbonates for the preparation of the plastics
composition according to the invention are all the known
polycarbonates. These are homopolycarbonates, copolycarbonates and
thermoplastic polyester carbonates.
The suitable polycarbonates preferably have average molecular
weights M.sub.w of from 10,000 to 50,000, preferably from 14,000 to
40,000 and in particular from 16,000 to 32,000, determined by gel
permeation chromatography with polycarbonate calibration. The
preparation of the polycarbonates is preferably carried out by the
interfacial process or the melt transesterification process, which
are described in many instances in the literature.
For the interfacial process, reference may be made by way of
example to H. Schnell, "Chemistry and Physics of Polycarbonates,
Polymer Reviews, vol. 9, Interscience Publishers, New York 1964 p.
33 et seq., to Polymer Reviews, vol. 10, "Condensation Polymers by
Interfacial and Solution Methods", Paul W. Morgan, Interscience
Publishers, New York 1965, chap. VIII, p. 325, to Dres. U. Grigo,
K. Kircher and P. R. Muller "Polycarbonate" in Becker/Braun,
Kunststoff-Handbuch, volume 3/1, Polycarbonate, Polyacetale,
Polyester, Celluloseester, Carl Hanser Verlag Munich, Vienna 1992,
p. 118-145 and to EP 0 517 044 A1.
The melt transesterification process is described, for example, in
the Encyclopedia of Polymer Science, vol. 10 (1969), Chemistry and
Physics of Polycarbonates, Polymer Reviews, H. Schnell, vol. 9,
John Wiley and Sons, Inc. (1964) and in the patent specifications
DE-B 10 31 512 and U.S. Pat. No. 6,228,973.
The polycarbonates are preferably prepared by reactions of
bisphenol compounds with carbonic acid compounds, in particular
phosgene, or, in the melt transesterification process, diphenyl
carbonate or dimethyl carbonate.
Homopolycarbonates based on bisphenol A and copolycarbonates based
on the monomers bisphenol A and
1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane are
particularly preferred here.
These and further bisphenol or diol compounds which can be employed
for the polycarbonate synthesis are disclosed inter alia in WO
2008037364 A1 (p. 7, 1. 21 to p. 10, 1. 5), EP 1 582 549 A1 ([0018]
to [0034]), WO 2002026862 A1 (p. 2, 1. 20 to p. 5, 1. 14), WO
2005113639 A1 (p. 2, 1. 1 to p. 7, 1. 20).
The polycarbonates can be linear or branched. Mixtures of branched
and unbranched polycarbonates can also be employed.
Suitable branching agents for polycarbonates are known from the
literature and are described, for example, in the patent
specifications U.S. Pat. No. 4,185,009 and DE 25 00 092 A1
(3,3-bis-(4-hydroxyaryl)-oxindoles according to the invention, see
in each case the entire document), DE 42 40 313 A1 (see p. 3, 1. 33
to 55), DE 19 943 642 A1 (see p. 5, 1. 25 to 34) and U.S. Pat. No.
5,367,044 and in the literature cited herein.
The polycarbonates used can moreover also be intrinsically
branched, no branching agent being added here in the context of the
polycarbonate preparation. An example for intrinsic branchings are
so-called Fries structures, such as are disclosed for melt
polycarbonates in EP 1 506 249 A1.
Chain terminators can furthermore be employed in the polycarbonate
preparation. Phenols, such as phenol, alkylphenols, such as cresol
and 4-tert-butylphenol, chlorophenol, bromophenol, cumylphenol or
mixtures thereof, are preferably used as chain terminators.
The thermoplastic polymer compositions according to the invention
based on the polymer component c) can optionally also contain
further components here, in addition to the organic colouring
agents or organic colouring agent combinations according to the
invention of components a) and b). These include:
d) optionally 0.000 wt. % to 0.015 wt. %, preferably 0.00150 wt. %
to 0.01500 wt. %, more preferably 0.00180 wt. % to 0.01100 wt. %
and particularly preferably 0.00200 wt. % to 0.00900 wt. % of at
least one organic or inorganic IR absorber, calculated as the
solids content of IR absorber in the total polymer composition. In
a specific embodiment, the IR absorbers are employed in an amount
of from preferably 0.00350 wt. % to 0.00850 wt. % and particularly
preferably 0.00400 to 0.00800 wt. %, calculated as the solids
content of IR absorber in the total polymer composition. In this
connection, solids content of IR absorber means the IR absorber as
the pure substance and not a suspension or other formulation
containing the pure substance.
Suitable IR absorbers are disclosed, for example, in EP 1 559 743
A1, EP 1 865 027 A1, DE 10022037 A1, DE 10006208 A1 and in the
Italian patent applications RM2010A000225, RM2010A000227 and
RM2010A000228.
Of the IR absorbers mentioned in the literature cited, those based
on boride and tungstate and ITO- and ATO-based absorbers and
combinations thereof are preferred.
e) optionally 0.00 wt. % to 20.00 wt. %, preferably from 0.05 wt. %
to 10.00 wt. %, more preferably from 0.10 wt. % to 1.00 wt. %,
still more preferably 0.10 wt. % to 0.50 wt. % and very
particularly preferably 0.10 wt. % to 0.30 wt. % of at least one UV
absorber.
Suitable UV absorbers are described, for example, in EP 1 308 084
A1, in DE 102007011069 A1 and in DE 10311063 A1.
f) optionally 0.0 wt. % to 5.0 wt. %, preferably 0.01 wt. % to 1.00
wt. % of at least one further additive. The further additives are
conventional polymer additives, such as e.g. the flameproofing
agents, optical brighteners, flow improvers, heat stabilizers,
inorganic pigments, mould release agents or processing auxiliaries
described in EP-A 0 839 623, WO-A 96/15102, EP-A 0 500 496 or
"Plastics Additives Handbook", Hans Zweifel, 5th edition 2000,
Hanser Verlag, Munich. In this connection, the substances already
disclosed as components a), b), d) and e) of the present invention
are expressly not a constituent of component f).
The polymer composition optionally contains an inorganic pigment,
preferably carbon black. The carbon black is preferably present in
the organic polymer matrix in finely dispersed form, and is
preferably nanoscale. Suitable carbon blacks have an average
particle size of preferably less than 100 nanometers (nm), more
preferably less than 75 nm, still more preferably less than 50 nm
and particularly preferably less than 40 nm, the average particle
size preferably being greater than 0.5 nm, more preferably greater
than 1 nm and particularly preferably greater than 5 nm. The
particle size is determined by TEM (transmission electron
microscopy).
g) optionally 0 wt. % to 50 wt. %, preferably 0 wt. % to 35 wt. %,
more preferably 0 wt. % to 30 wt. %, particularly preferably 10 wt.
% to 30 wt. % of fillers and reinforcing substances.
Fillers and reinforcing substances for polymer compositions are
described, for example, in EP 1 624 012 A1, DE 3742881 A1, U.S.
Pat. No. 6,860,539 B2, US 20060105053 A1, DE 102006055479 A1, WO
2005030851 A1 and in WO 2008122359 A1.
The amounts stated above in each case relate to the total polymer
composition.
The coloured thermoplastic polymer compositions according to the
invention contain at least one colouring agent or one colouring
agent combination of the colouring agents and combinations
disclosed under I to XXVI.
Preferably, the coloured thermoplastic polymer compositions
according to the invention contain a combination of organic
colouring agents according to the invention, wherein the organic
colouring agent combinations according to the invention comprise at
least one colouring agent chosen from the structures given for
component a) and at least one colouring agent chosen from the
structures given for component b).
More preferably, the colouring agent combinations which have
already emerged as particularly suitable in the context of the
present disclosure are explicitly used in the coloured
thermoplastic polymer compositions according to the invention. In
this context, the explicit colouring agent structures mentioned as
preferred among the components a) and b) are correspondingly
preferably employed in these particularly suitable colouring agent
combinations.
The composition must be processable under the conventional
temperatures for thermoplastics, i.e. at temperatures above
300.degree. C., such as e.g. 350.degree. C., without the colour or
the performance data changing significantly during processing.
The preparation of the polymer compositions according to the
invention containing the components a) to g) is carried out with
the usual processes of incorporation by bringing together, mixing
and homogenizing, the homogenizing in particular preferably taking
place in the melt under the action of shearing forces. The bringing
together and mixing are optionally carried out before the melt
homogenization, using powder premixes.
Premixes which have been prepared from solutions of the mixing
components in suitable solvents, homogenization optionally being
carried out in solution and the solvent then being removed, can
also be used.
In particular, the components of the composition according to the
invention can be introduced here by known processes, such as, inter
alia, as a masterbatch.
The use of masterbatches and of powder mixtures or compacted
premixes is suitable in particular for introduction of the
components a), b), e) and f). All the abovementioned components can
optionally be premixed here. Alternatively, however, premixes of a)
and b) or of a), b) and d) and any desired other combinations are
also possible. In all cases, for better ease of metering in the
preparation of the thermoplastic polymer compositions, the
abovementioned component premixes are preferably topped up with
pulverulent polymer component c) such that total volumes which are
easy to handle arise.
In a particular embodiment, the abovementioned components can be
mixed to form a masterbatch, the mixing preferably taking place in
the melt under the action of shearing forces (for example in a
kneader or twin-screw extruder). This process offers the advantage
that the components are distributed better in the polymer matrix.
For preparation of the masterbatch, the thermoplastic which is also
the main component of the final total polymer composition is
preferably chosen as the polymer matrix.
In this connection, the composition can be brought together, mixed,
homogenized and then extruded in conventional devices, such as
screw extruders (for example twin-screw extruders, TSE), kneaders
or Brabender or Banbury mills. After the extrusion, the extrudate
can be cooled and comminuted. Individual components can also be
premixed and the remaining starting substances can then be added
individually and/or likewise as a mixture.
The polymer compositions according to the invention can be
processed to products or shaped articles for example by first
extruding the polymer compositions to granules, as described, and
processing these granules to various products or shaped articles by
suitable processes in a known manner.
In this connection, the compositions according to the invention can
be converted into products, shaped articles or shaped objects, for
example, by hot pressing, spinning, blow moulding, thermoforming,
extrusion or injection moulding. The use of multi-layer systems is
also of interest. The application can be effected at the same time
as or immediately after the shaping of the base body, e.g. by
coextrusion or multi-component injection moulding. However, the
application can also be effected on the ready-formed base body,
e.g. by lamination with a film or by coating with a solution.
Sheets or shaped articles of a base and optional top layer/optional
top layers (multilayer systems) can be produced by (co)extrusion,
direct skinning, direct coating, insert moulding, back-injection
moulding of films or other suitable processes known to the person
skilled in the art.
Injection moulding processes are known to the person skilled in the
art and are described, for example, in "Handbuch Spritzgiessen",
Friedrich Johannnaber/Walter Michaeli, Munich; Vienna: Hanser,
2001, ISBN 3-446-15632-1 or "Anleitung zum Bau von
Spritzgiesswerkzeugen", Menges/Michaeli/Mohren, Munich; Vienna:
Hanser, 1999, ISBN 3-446-21258-2.
Extrusion processes are known to the person skilled in the art and
are described, for example for coextrusion, inter alia in EP-A 0
110 221, EP-A 0 110 238 and EP-A 0 716 919. For details of the
adapter and die process see Johannaber/Ast:
"Kunststoff-Maschinenfuhrer", Hanser Verlag, 2000 and in
Gesellschaft Kunststofftechnik: "Coextrudierte Folien und Platten:
Zukunftsperspektiven, Anforderungen, Anlagen und Herstellung,
Qualitatssicherung", VDI-Verlag, 1990.
Products, shaped articles or shaped objects which are preferred
according to the invention are glazing, for example automobile
windows, windows of track vehicles and aircraft, automobile
sunroofs, safety screens, roofing or building glazing, LEDs, lamp
covers for the interior area of vehicles and buildings, lamp covers
for outdoors, such as e.g. covers of streetlights, sighting
devices, spectacles, extruded and solvent films for displays or
electric motors, also ski foils, traffic light lenses, which
contain the compositions according to the invention. In this
context, in addition to solid sheets, twin-wall sheets or
multi-wall sheets can also be used. As further components of the
products according to the invention, in addition to the
compositions according to the invention, the products according to
the invention can contain, for example, further material parts.
In a particular embodiment, the articles produced from the
composition of the present invention are coated. This coating
serves to protect the thermoplastic material from general
weathering influences (e.g. damage by sunlight) and from mechanical
impairment of the surface (e.g. scratching) and thus increases the
resistance of the correspondingly treated articles.
It is known that polycarbonate can be protected from UV radiation
by means of various coatings. These coatings conventionally contain
UV absorbers. These layers likewise increase the scratch resistance
of the corresponding article. The articles from the present
invention can carry one layer or multi-layer systems. They can be
coated on one or both sides. In a preferred embodiment, the article
contains a scratch-resistant lacquer containing UV absorbers. In a
particular embodiment, the multi-layer product comprises at least
one layer containing the composition according to the invention, at
least one UV protective layer and optionally a scratch-resistant
coating.
In the case of glazing materials, the article carries at least one
scratch-resistant and/or antireflex coating on at least one
side.
EXAMPLES
The invention is described in more detail with the aid of
embodiment examples in the following, the determination methods
described here being used for all the corresponding parameters in
the present invention if nothing to the contrary had been
described.
Melt Volume Rate:
The melt volume rate (MVR) is determined in accordance with ISO
1133 (at 300.degree. C.; 1.2 kg).
The colour in transmission is determined with a Lambda 900
spectrophotometer from Perkin Elmer with a photometer sphere in
accordance with ASTM E1348 with the weighting factors and formulae
described in ASTM E308.
The CIELAB colour coordinates L*, a*, b* are calculated for light
type D 65 and 10.degree. normal observer.
Light Transmission (Ty):
The transmission measurements were performed on a Lambda 900
spectrophotometer from Perkin Elmer with a photometer sphere in
accordance with ISO 13468-2 (i.e. determination of the total
transmission by measurement of the diffuse transmission and direct
transmission).
Colour Change:
.DELTA.E is a calculated value for the colour difference detected
in accordance with ASTM D 2244. In the present experiments, light
type D 65/10.degree. was used. Formula 7 in ASTM D 2244 was used
for calculation of the .DELTA.E value.
Weathering:
The artificial weathering with exposure to xenon light is carried
out in accordance with the standard ASTM G 155 in a xenon CI-5000
weatherometer from Atlas on coloured sample sheets (see production
of the test specimens). Two borosilicate filters were used as UV
filters. The incident radiation intensity is 0.75 W/m.sup.2/nm at
340 nm. The black standard temperature is 80.degree. C., the sample
room temperature 40.degree. C. The samples are irrigated for 18 min
every 120 min, the exposure to light also remaining switched on
during the irrigation phase. The abovementioned weathering method
is called Xe-Wom 0.75 W in the following.
Visual Colour Impression:
The visual colour impression is determined with the naked eye with
the aid of coloured sample sheets (see production of the test
specimens). For this, the coloured sample sheets were viewed in
daylight against a white background and classified accordingly (for
the classification see the table Test specimens and measurement
results).
Clouding:
The clouding was determined in accordance with ASTM D 1003 with a
BYK Gardner Haze Gard.
Materials for production of the test specimens:
Component a) The product from A (all R.dbd.H, see below) is used as
the colouring agent of the formula (1a, 1b). The product from B
(all R.dbd.H, see below) is used as the colouring agent of the
formula (2a, 2b). Macrolex Violet B (Solvent Violet 13, CAS No.
81-48-1) from Lanxess AG, Leverkusen is used as the colouring agent
of the formula (3).
Component b) Macrolex Red EG (Solvent Red 135, CAS No. 20749-68-2)
from Lanxess AG, Leverkusen is used as the colouring agent of the
structure (4). Paliogen Blue 6385 (Pigment Blue 60, CAS No.
81-77-6) from BASF SE, 67065 Ludwigshafen, Germany is used as the
colouring agent of the structure (7). This colouring agent has a
bulk volume of 7 l/kg, a pH of 6-9 and a specific surface area of
40 m.sup.2/g. Heliogen Blue K 6911 D (CAS No. 147-14-8) from BASF
SE, 67065 Ludwigshafen, Germany is used as the colouring agent of
the structure (8b).
Component c) Linear bisphenol A polycarbonate with end groups based
on phenol with a melt volume rate (MVR) of 6 cm.sup.3/10 min
(measured at 300.degree. C. under a 1.2 kg load in accordance with
ISO 1033), called PC 1 in the following. Linear bisphenol A
polycarbonate with end groups based on phenol with an MVR of 12.5
cm.sup.3/10 min (measured at 300.degree. C. under a 1.2 kg load in
accordance with ISO 1033), called PC 2 in the following. PC 2 also
contains an additive mixture comprising mould release agent, heat
stabilizer and UV stabilizer. Pentaerythritol tetrastearate (CAS
115-83-3) is employed as the mould release agent,
triphenylphosphine (CAS 603-35-0) is employed as the heat
stabilizer and Tinuvin.RTM. 329 (CAS 3147-75-9) is employed as the
UV stabilizer.
Component d) Lanthanum hexaboride, LaB.sub.6 (KIDS 06 from Sumitomo
Metal Mining, Japan, CAS No. 857255-66-4). The product is in the
form of a pulverulent dispersion. The weights stated in the
examples relate to the product KHDS 06, the solids content of
lanthanum hexaboride in the commercial KHDS 06 dispersion employed
being 21.5 wt. %. Lanthanum hexaboride, LaB.sub.6 (KHDS 872G2 from
Sumitomo Metal Mining, Japan, CAS. No. 949005-03-2). The product is
in the form of a pulverulent dispersion. The weights stated in the
examples relate to the product KHDS 872G2, the solids content of
lanthanum hexaboride in the commercial KHDS 872G2 dispersion
employed being 10.0 wt. %. Lumogen IR 765 (a quaterrylene, CAS No.
943969-69-5) from BASF SE, 67065 Ludwigshafen, Germany A
pulverulent dispersion (FMDS 874 from Sumitomo Metal Mining, Japan,
polyacrylate dispersion, CAS No. 953384-75-3) was employed as an ER
absorber based on ATO, the solids content of SnO.sub.2:Sb in the
dispersion being 25 wt. %.
Component f) Black Pearls.RTM. 800 (CAS No. 1333-86-4) from Cabot
Corp. are employed as nanoscale carbon black (particle size approx.
17 nm).
Colouring Agents for Comparison Examples
Macrolex Blue RR (Colour Index: Solvent Blue 97; CAS No.:
32724-62-2) from Lanxess Deutschland GmbH is employed as a further
colouring agent which is not according to the invention.
Macrolex Violet 3R Gran. (Colour index: Solvent Violet 36; CAS No.:
61951-89-1) from Lanxess Deutschland GmbH is employed as a further
colouring agent which is not according to the invention.
Preparation of the Thermoplastic Polymer Compositions by
Compounding:
The compounding of the additives was carried out on a twin-screw
extruder from KraussMaffei Berstorff, type ZE25 at a housing
temperature of 260.degree. C. and a melt temperature of 270.degree.
C. at a speed of rotation of 100 rpm at a throughput of 10 kg/h
with the amounts of components stated in the examples. For better
mixing, a powder mixture of PC 1 (10 wt. % of powder mixture, based
on the total composition) containing the further components stated
below is first prepared here. This powder mixture is metered into
PC 2 during the compounding.
Production of the Test Specimens:
The granules are dried in vacuo at 120.degree. C. for 3 hours and
then processed on an injection moulding machine of the Arburg 370
type with a 25 injection unit at a melt temperature of 300.degree.
C. and a mould temperature of 90.degree. C. to give coloured sample
sheets with the dimensions 60 mm.times.40 mm.times.Z mm; Z here is
3.2 mm, 4.0 mm or 5.0 mm.
Preparation of the Substances of Component a)
Inter alia, structures of the formula (1a), (1b), (2a) and (2b)
were employed in the examples according to the invention. The
preparation of these dyestuffs was carried out in accordance with
DE 2148101 as follows:
Preparation of a 1:1 Mixture (Wt. %) of (1a) and (1b):
5.62 g (0.025 mol) of benzene-1,2,4,5-tetracarboxylic acid
dianhydride and 7.99 g (0.05 mol) of 1,8-diaminonaphthalene are
initially introduced into 75 ml of M-ethylpyrrolidone at room
temperature and the mixture is heated slowly to 150.degree. C. It
is stirred at this temperature for 5 hours. After cooling, 125 ml
of water are added and the precipitate which has precipitated out
is filtered off. The precipitate is suspended in water several more
times and washed in this manner. The precipitate is dried at
80.degree. C. under a high vacuum. A mixture of 50 ml of glacial
acetic acid and 25 ml of acetic anhydride is added to the dried
precipitate. The mixture is boiled under reflux for 4 hours. After
cooling, the reaction mixture is added to 500 ml of water. The
precipitate is filtered off, washed with water and dried at
80.degree. C. under a high vacuum. 12.5 g of a lilac-coloured
powder are obtained.
B. Preparation of a 1:1 Mixture (wt. %) of (2a) and (2b):
6.71 g (0.025 mol) of naphthalene-1,4,5,8-tetracarboxylic acid
dianhydride and 7.99 g (0.05 mol) of 1,8-diaminonaphthalene are
initially introduced into 75 ml of M-ethylpyrrolidone at room
temperature and the mixture is heated slowly to 150.degree. C. It
is stirred at this temperature for 5 hours. After cooling, 152 ml
of water are added and the precipitate which has precipitated out
is filtered off. The precipitate is suspended in water several more
times and washed in this manner. The precipitate is dried at
80.degree. C. under a high vacuum. A mixture of 50 ml of glacial
acetic acid and 25 ml of acetic anhydride is added to the dried
precipitate. The mixture is boiled under reflux for 4 hours. After
cooling, the reaction mixture is added to 125 ml of water. The
precipitate is filtered off, washed with hot water and dried at
80.degree. C. under a high vacuum. 13.7 g of a lilac-coloured
powder are obtained.
Lacquering of the Test Specimens:
The product SHP470FT (Momentive Performance Materials Inc. Wilton,
Conn. USA) is used as the primer. The product AS 4700 (Momentive
Performance Materials Inc. Wilton, Conn. USA) is used as the
protective lacquer.
The coating was carried out in a climatically controlled coating
room under the particular instructions of the lacquer manufacturer
at 23 to 25.degree. C. and 40 to 48% rel. humidity.
The test specimens were cleaned with so-called iso-cloths
(LymSat.RTM. from LymTech Scientific; saturated with 70%
isopropanol and 30% deionized water), rinsed with isopropanol,
dried in air for 30 min and blasted with ionized air.
The test specimens are coated by hand by the flooding process. In
this case, the primer solution is poured over the sheet in the
longitudinal direction starting from the upper edge of the small
part, while at the same time the starting point of the primer on
the sheet is guided from left to right over the sheet width. The
primed sheet was dried in air until dust dry and cured in a
circulating air oven according to the particular manufacturer's
instructions, while suspended vertically on a clamp (dried in air
at room temperature for 30 minutes and cured at 125.degree. C. for
30 minutes). After cooling to room temperature, coating of the
primed surface with AS 4700 was carried out. After the drying in
air until dust dry, curing was carried out at 130.degree. C. in a
circulating air oven for 60 min.
The primer layer thickness and the thickness of the topcoat can
influence the weathering properties.
In order to achieve a sufficient and comparable protective action
against weathering, the primer layer thickness for the following
examples should be in the range of 1.2-4.0 .mu.m and the thickness
of the topcoat should be between 4.0 and 8.0 .mu.m. In the
following table of results, the primer layer thickness is stated
before the forward slash and the thickness of the topcoat is stated
after the forward slash in the topcoat column.
Example 1
Comparison Example
A polymer composition containing the amounts of the following
components is prepared by compounding as described above.
TABLE-US-00001 Macrolex Red EG (component b)): 0.00313 wt. %
Macrolex Blue RR (colouring agent 0.00320 wt. % for comparison
examples): Lumogen IR 765 (component d)): 0.00180 wt. % KHDS 06
(component d)): 0.01350 wt. % BlackPearls 800 (component f)):
0.00144 wt. % PC 1 (component c)): 9.97693 wt. % PC 2 (component
c)): 90.00000 wt. %
PC 2 here contains the additives listed above under PC 2. PC 2 here
contains 0.270 wt. % of mould release agent, 0.025 wt. % of heat
stabilizer and 0.200 wt. % of UV stabilizer, in each case based on
the amount of PC 2 employed.
Example 2
Comparison Example
A polymer composition containing the amounts of the following
components is prepared as described above:
TABLE-US-00002 Macrolex Red EG (component b)): 0.00335 wt. %
Macrolex Blue RR (colouring agent 0.00315 wt. % for comparison
examples): Lumogen IR 765 (component d)): 0.00140 wt. % KHDS 872G2
(component d)): 0.06000 wt. % BlackPearls 800 (component f)):
0.00128 wt. % PC 1 (component c)): 9.93082 wt. % PC 2 (component
c)): 90.00000 wt. %
PC 2 here contains the additives listed above under PC 2. PC 2 here
contains 0.270 wt. % of mould release agent, 0.025 wt. % of heat
stabilizer and 0.200 wt. % of UV stabilizer, in each case based on
the amount of PC 2 employed.
Example 3
Comparison Example
A polymer composition containing the amounts of the following
components is prepared as described above:
TABLE-US-00003 Macrolex Red EG (component b)): 0.002450 wt. %
Macrolex Blue RR (colouring agent 0.003090 wt. % for comparison
examples): Heliogen Blue K6911D (component b)): 0.000095 wt. % KHDS
872G2 (component d)): 0.057000 wt. % BlackPearls 800 (component
f)): 0.001410 wt. % PC 1 (component c)): 9.935955 wt. % PC 2
(component c)): 90.000000 wt. %
PC 2 here contains the additives listed above under PC 2. PC 2 here
contains 0.270 wt. % of mould release agent, 0.025 wt. % of heat
stabilizer and 0.200 wt. % of UV stabilizer, in each case based on
the amount of PC 2 employed.
Example 4
Comparison Example
A polymer composition containing the amounts of the following
components is prepared as described above:
TABLE-US-00004 Macrolex Red EG (component b)): 0.00550 wt. %
Macrolex Blue RR (colouring agent 0.00392 wt. % for comparison
examples): Heliogen Blue K6911D (component b)): 0.00133 wt. % KHDS
06 (component d)): 0.03130 wt. % BlackPearls 800 (component f)):
0.00167 wt. % PC 1 (component c)): 9.95628 wt. % PC 2 (component
c)): 90.00000 wt. %
PC 2 here contains the additives listed above under PC 2. PC 2 here
contains 0.270 wt. % of mould release agent, 0.025 wt. % of heat
stabilizer and 0.200 wt. % of UV stabilizer, in each case based on
the amount of PC 2 employed.
Example 5
Comparison Example
A polymer composition containing the amounts of the following
components is prepared as described above:
TABLE-US-00005 Macrolex Red EG (component b)): 0.00370 wt. %
Macrolex Violet 3R Gran (colouring agent 0.00240 wt. % for
comparison examples): Heliogen Blue K6911D (component b)): 0.00230
wt. % KHDS 06 (component d)): 0.03000 wt. % BlackPearls 800
(component f)): 0.00065 wt. % PC 1 (component c)): 9.96095 wt. % PC
2 (component c)): 90.00000 wt. %
PC 2 here contains the additives listed above under PC 2. PC 2 here
contains 0.270 wt. % of mould release agent, 0.025 wt. % of heat
stabilizer and 0.200 wt. % of UV stabilizer, in each case based on
the amount of PC 2 employed.
Example 6
Comparison Example
A polymer composition containing the amounts of the following
components is prepared as described above:
TABLE-US-00006 Macrolex Red EG (component b)): 0.00470 wt. %
Macrolex Violet 3R Gran (colouring agent 0.00117 wt. % for
comparison examples): Heliogen Blue K6911D (component b)): 0.00262
wt. % YMDS 874 (component d)): 0.10000 wt. % BlackPearls 800
(component f)): 0.00188 wt. % PC 1 (component c)): 9.88963 wt. % PC
2 (component c)): 90.00000 wt. %
PC 2 here contains the additives listed above under PC 2. PC 2 here
contains 0.270 wt. % of mould release agent, 0.025 wt. % of heat
stabilizer and 0.200 wt. % of UV stabilizer, in each case based on
the amount of PC 2 employed.
Example 7
According to the Invention
A polymer composition containing the amounts of the following
components is prepared as described above:
TABLE-US-00007 Paliogen Blue L6385 (component b)): 0.00210 wt. % A.
1:1 mixture (wt. %) of (1a) and (1b) 0.00147 wt. % (component a)):
KHDS 872G2 (component d)): 0.07500 wt. % BlackPearls 800 (component
f)): 0.00165 wt. % PC 1 (component c)): 9.91978 wt. % PC 2
(component c)): 90.00000 wt. %
PC 2 here contains the additives listed above under PC 2. PC 2 here
contains 0.270 wt. % of mould release agent, 0.025 wt. % of heat
stabilizer and 0.200 wt. % of UV stabilizer, in each case based on
the amount of PC 2 employed.
Example 8
According to the Invention
A polymer composition containing the amounts of the following
components is prepared as described above:
TABLE-US-00008 Paliogen Blue L6385 (component b)): 0.00278 wt. %
1:1 mixture (wt. %) of (1a) and (1b) (component a)): 0.00236 wt. %
KHDS 872G2 (component d)): 0.07000 wt. % BlackPearls 800 (component
f)): 0.00220 wt. % PC 1 (component c)): 9.92266 wt. % PC 2
(component c)): 90.00000 wt. %
PC 2 here contains the additives listed above under PC 2. PC 2 here
contains 0.270 wt. % of mould release agent, 0.025 wt. % of heat
stabilizer and 0.200 wt. % of UV stabilizer, in each case based on
the amount of PC 2 employed.
Example 9
According to the Invention
A polymer composition containing the amounts of the following
components is prepared as described above:
TABLE-US-00009 Paliogen Blue L6385 (component b)): 0.00211 wt. %
1:1 mixture (wt. %) of (1a) and (1b) (component a)): 0.00248 wt. %
KHDS 872G2 (component d)): 0.09000 wt. % FMDS 874 (component d)):
0.12552 wt. % BlackPearls 800 (component f)): 0.00139 wt. % PC 1
(component c)): 9.77850 wt. % PC 2 (component c)): 90.00000 wt.
%
PC 2 here contains the additives listed above under PC 2. PC 2 here
contains 0.270 wt. % of mould release agent, 0.025 wt. % of heat
stabilizer and 0.200 wt. % of UV stabilizer, in each case based on
the amount of PC 2 employed.
TABLE-US-00010 TABLE 1 Test specimens and measurement results
Visual Primer/ .DELTA.E .DELTA.E .DELTA.E colour Visual Thickness *
Topcoat * 1,000 2,000 3,000 impression colour Example [mm] [.mu.m]
h ** h ** h ** 3,000 h ** impression *** 1 5.0 2.2/5.1 1.89 3.41
4.76 - + (comparison) 2 5.0 1.7/5.6 1.88 3.60 5.10 - + (comparison)
3 5.0 1.4/5.4 1.85 3.69 5.11 - + (comparison) 4 3.2 1.8/4.3 3.01
5.30 7.29 -- + (comparison) 5 3.2 1.3/6.1 1.50 2.73 3.77
.largecircle. + (comparison) 6 4.0 2.8/4.2 1.44 2.64 3.71
.largecircle. + (comparison) 7 5.0 1.6/6.1 0.82 1.34 1.74 + +
(according to the invention) 8 3.2 1.4/6.4 0.94 1.29 1.69 + +
(according to the invention 9 3.2 1.5/6.3 1.02 1.80 2.91 + +
(according to the invention * Data on the test specimen; ** after
weathering; *** before weathering + pleasant; .largecircle.
adequate; - poor; -- very poor
Overall, it is to be said that only the mixtures according to the
invention have the required colour stability (.DELTA.E).
The comparison examples show that the colouring agents cannot be
combined as desired. Comparison Examples 1 to 6 indeed show a
similar colour impression to the examples according to the
invention. Nevertheless, these examples show a significant and
undesirable colour shift after weathering. Even when the comparison
examples in some cases contain colouring agents which are also used
in the compositions according to the invention, these are not
stable to weathering. It is thus found, surprisingly, that only the
use of the colouring agent combinations according to the invention
leads to the desired colour-stable polymer compositions.
It will be appreciated by those skilled in the art that changes
could be made to the embodiments described above without departing
from the broad inventive concept thereof. It is understood,
therefore, that this invention is not limited to the particular
embodiments disclosed, but it is intended to cover modifications
within the spirit and scope of the present invention as defined by
the appended claims.
* * * * *